Triazine phosphorus compounds



Patented Apr. 7, 1 953 4 UNITED STATES PATENT. OFFICE TRIAZINE PHQSPHORUS COMPOUNDS Morris L. Nielsen, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application December 29, 1950,

' Serial No. 203,555

,bustible fibers in a'form insoluble in water to resist washing and weathering. The various inorganic phosphorus salts are therefore generally disadvantageous, as are the salts formed by melamine with acids since such'compounds are generally soluble in water so that they are readily washed out of a fabric;

It has now been discovered that a water-insoluble phosphorus-containing triazine composition may be obtained as the compound ammelino phosphoryl dichloride obtained by the reaction of ammeline and phosphorus oxychloride. The resulting material is clearly nota phosphate, but is instead a new compound which is generally insoluble in organic and inorganic solvents. Even .strongacids, do not dissolve this substance, short of extensively decomposing the material. It has also been found that ammelino phosphoryl dichloride may be reacted with ammonia to give ammelino phosphoryl diamide. This reaction may be carried out at room temperature or at elevated temperatures in the presence of anhydrous or aqueous ammonia.

In a specific embodiment of the proces of the present invention to produce the novel composition, the following examples illustrate the details of the process.

Example 1 The compound ammelino phosphoryl dichloride was produced by mixing 0.5 gm. mole of ammeline with one gm. mole of phosphorus'oxychloride. The mixture of these components was heated at refluxing temperatur in a reaction flask provided with" a'stirrer. The reaction mix- ,ture was then cooled and was washed with-berrzene to remove unreacted phosphorus oxychlo- ,ride. The remaining crude product was dried for an hour under vacuum'to give "g. of a powdery material. The product was insoluble in water and appeared to have a structure corresponding to a mono-phosphorylation as is shown in the formula below:

The material was found to be amorphous'without any evidence of crystallinity.

In general, the composition of matter resulting from the above reaction of ammeline and phosphorus oxychloride may be prepared by the thermal reaction of these two components; It has been found that at least one mole of phosphorus oxychloride may be used for each mole of ammeline. Such mixtures'in the above range of proportions of the two ingredients may be blended together and the mixture may then be added at a reflux temperature of about 108 in :order tocar 'y out the reaction. In general, the temperature is not critical, although the range of 200' C, is preferred. The time of reaction is not critical, as a satisfactory product is obtained when the reactants are maintained at a reflux temperature for a period sufiicient to permit completionof the reaction which may be approximately 2-6 hours. The reaction may be carried out at atmospheric pressure, such as in open vessels, or under pressure in..an autoclave. -Avariation ofthe' above process may be carried out by conducting the reaction in an organic solvent for phosphoryl chloride, e. g., benzene or kerosene.

Example 2 The ammelino phosphoryl dichloride obtained by the aboveg'process: was treated withliquid'ammom'a in apressure vessel at room temperature.

The two components were left together for a day, after which the vessel was opened. It was found" that the new product obtained: insubstantial:

yield was ammeline phosphoryl diamide This compound was also insoluble inwater and organic solvents .generall'y. Theproduct was obtained as ,a white powder which .could be, suspended, in, water.

The compositions obtained by the, above processes of Examples 1 and 2 may be used as a fertilizer ingredient. In this relationship it is of yalue -b'ecauseiof its .highconcentration of :nitrogen andtphosphorus which, in theform of the substantially. insoluble-complex are made. slowly available. to plant a growth.

xample 3 The useo'f" the above ammeline phosphoryl di- .:c l" l l oride derived from ammeline and phosphorus 'oxychloride is-shown as a flameproofing composition in, this example.- A sheeting'grade cotton was treated by applying a water suspension none-aqueous. suspensions, if1desired.

Example: 4

Ammelino phosphoryl diamide was subjected to the same test asdescribediiri Example .3. The test :sample of cotton sheeting showed a. char length of 6.0. inches, showing that the, treated 1 sample resisted burning.

The-.above compositionsofthe present invention are. obtained-as. a White to greys-colored .powderwhich mayalsobe employed as a deluslterantlin the fabric of certain resinsand plastic materials. 'Sincethe products arev amorphous,

they may bereadily blended and combined with other ingredients to provide a, smooth, composition free from, roughness. su-ch as. would otherwise'rresult in theemploymentof roughly crystalline. materials.

Example '5 .Anothergnewr-compound whichwan bezprepa-red from the chloride of Example 1 is ammelino phosphoric acid This compound can be prepared by hydrolyzing ammelin'o'phosphoryl dichloride, such as by prolonged boiling or by treatment with dilute alkali. The latter' may be an aqueous solution .ofjsodium'or potassium carbonate or hydroxide.

The, alkali treatment is preferably followed by acidification to obtain the acid. The ammelino phosphoric acid is moderately water-soluble.

Although the specific examples illustrate the reaction of'ammeline, which is'a mono-hydroxy compound; it is also within the-scope'of theinvention to react ammelidewith phosphorus oxychloride. Ammelide is a dihydroxy compound which is called 6-amino-s-triazine-2,4-diol. 7

Having now described certain specific forms of theinvention, it is to be understood that the invention is not to be limited to the specific forms or compositions herein described or' specifically covered by'the claims.

What is claimed'and is desiredto be protected by'Letters Patent of the UnitedStates is:

1. Ammelino'phosp'horyl dichloride- 2; The process for manufacturing 'ammelin'o phosphoryl chloride havingthe formula:

3. The. process of manufacturing ammeline phosphorylchloride having the formula:

which comprises heating together: 1 to 2: moles of phosphorus: oxychloride and one molezofiamiznelineto aitemperaturein:theirange. of C; to 00b0,.

*which comprises heating a mixture of 3 moles of 5 6 4. The process of manufacturing ammeline 6. The process of manufacturing ammelino phosphoryl chloride having the formula: phosphoryl diamide having the formula:

NH: o1 ne 5 (mm o 01 i & A N/ \N n B I 10 NHr- C-NH: NHr- -NH:

contacting of ammelino phosphoryl dichloride with ammonia.

phosphorus oxychloride and one mole of '7. Ammeline substitution products having the meline to a temperature corresponding to the composltlon: boiling point of the said mixture. 5. Ammelino phosphoryl diamide l:\

X /NH2 A: N \N O NH: 4: g 6 NH: --NH2 a ll where X is a radical selected from the group consisting of --Cl and -NH2 radicals.

N MORRIS L. NIELSEN.

No references cited. 

7. AMMELINE SUBSTITUTION PRODUCTS HAVING THE COMPOSITION: 